US3881047A - Treatment of fibres - Google Patents

Treatment of fibres Download PDF

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Publication number
US3881047A
US3881047A US37540873A US3881047A US 3881047 A US3881047 A US 3881047A US 37540873 A US37540873 A US 37540873A US 3881047 A US3881047 A US 3881047A
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Prior art keywords
polythiol
fibres
formula
zero
alkylene
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Derek James Rowland Massy
Kenneth Winterbottom
Albert John Barber
James Mccartney
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Novartis AG
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Ciba Geigy AG
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Priority to GB3224170A priority Critical patent/GB1358837A/en
Priority to CH952571A priority patent/CH547894A/xx
Priority to CH952571D priority patent/CH952571A4/xx
Priority to DE19712132535 priority patent/DE2132535A1/de
Priority to FR7124053A priority patent/FR2100853B1/fr
Priority to AT570571A priority patent/AT322494B/de
Priority to NL7109109A priority patent/NL7109109A/xx
Priority to BE769410A priority patent/BE769410A/xx
Priority to CA117,208A priority patent/CA967710A/en
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Priority to US37540873 priority patent/US3881047A/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3342—Polymers modified by chemical after-treatment with organic compounds containing sulfur having sulfur bound to carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2938—Coating on discrete and individual rods, strands or filaments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31533—Of polythioether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • This invention relates to a process for modifying synthetic materials in fibrous form, and to materials so treated.
  • softening agents such as (1) polyethylene emulsions, (2) adducts of ethylene oxide with phenols or emines, and (3) cationic compounds such as C -C fatty amine or aminoamide salts.
  • the softener is preferably applied to the wet fabric just after dyeing and it is highly desirable that it exhausts on to it. Many conventional agents fail in this respect, and even when exhaustion does occur, it is incomplete, a high proportion of the softener being wasted. Furthermore, a considerable amount of the softener is lost on washing the fabric.
  • the present invention provides a process for modifying synthetic fibres which comprises 1. treating the fibres, in the absence of keratinous material, with a polythiol having at least two thiol groups per molecule and containing a. a radical of a polyhydric alcohol,
  • the present invention further provides synthetic fibrous materials, in the absence of keratinous materials, bearing thereon a polythiol as aforesaid in the cured or still curable state.
  • the polythiol may be used in conjunction with an aminoplast, in which case treatment with, and curing, the aminoplast and the polythiol, can take place in any desired sequence.
  • the fibres may be impregnated with a mixture of the aminoplast and the polythiol, and then the aminoplast and polythiol are cured.
  • the fibres may be impregnated first with the polythiol and then with the aminoplast, or vice versa, and then the aminoplast and polythiol are cured.
  • an aminoplast can be cured on the fibres, which are then treated with the polythiol and the polythiol is cured.
  • epoxide res- Synthetic fibres which may be subjected to the process of the present invention may be in the form of loose fibres, yarns, threads, woven, non-woven and knitted fabrics and garments, and woven and tuftcd carpets, needle-punched and other mechanical'y formed fibrous floor-covering materials, and are preferably polyamides (nylons), polyesters, polyacrylonitriles, and polyvinyl alcohols.
  • synthetic fibres is taken herein to include man-made fibres of cellulosic origin in which all three available hydroxyl groups per anhydrogluco unit have been chemically modified, e.g., by acylation, etherificatiom'or cyanoethylation.
  • cellulose triacetate is regarded, for the purpose of this invention, as a synthetic material.
  • Polythiols used in the process of this invention contain two, three, and preferably not more than six, thiol groups per molecule. Especially good results have been obtained with those containing two or three thiol groups per molecule.
  • Preferred polythiols are those having a molecular weight between 400 and 10,000 particularly those of formula '1 -"r -(-Oalkylene OH i- R j q -(O-alkylene) O (CO) n X l in which m is an integer of at least 1 and may have different values in each of the p and q chains,
  • n zero or 1
  • p is a positive integer of at least 2 and at most 6 q is zero or a positive integer of 4 or less, selected so that (p-l-q) equals at least 2 and at most 6,
  • each alkylene group contains a chain of at least 2 and at most 6 carbon atoms between consecutive oxygen atoms
  • R represents an aliphatic radical containing at least 2 carbon atoms
  • X represents an aliphatic radical containing at least one thiol group.
  • the oxyalkylene units in individual poly(oxyalkylene) chains may be different. They may be substituted, if desired, by e.g., phenyl or chloromethyl groups.
  • esters of the formula CH H CH I (OC H O.COC H SH -(-O--alkenylene-)- OH R1 q CIZH b (OC H O.CO.C H SH CH (0C Hzt) OH (Oalkylene-)- O.CO.C H- SH t m 'CH (OC H O.CO.C H SH P in which alkylene, m, p, and q have the meanings previously assigned,
  • esters of formula l (CH2) 2 l l l 7 CH (OC H O.CO.C H SH I (O-alkylene) OH 2 H m (O-alkylene) O.CO.C H SH T Qm p i 2 3O CH (OC H O.CO.C H SH 2 R ⁇ (O alkylene) OCOC H SH and 2 T and CH CH- OCH H O.CO.C H SH R o-alkylene) OCOC H SH 3 l t 2t u 2u.
  • R represents an aliphatic hydrocarbon radical hav- H (O (CH 4 OCOCH SH ing at least 3 and at most 6 carbon atoms. 7
  • Polythiol esters most preferred for the purposes of the present invention are those obtained from glycerol CH O z or propylene glycol, propylene oxide, and thioglycollic acid, i.e., of formula TH (oc n O.CO.C H SH CH (0C H O CO c H SH CH2 (oc n ococn sn 2 t 2t m o u CH (OC H ococn sn CH (oc n O.CO.C H SH l m CH2 (OC H ococn sn having a molecular weight within the range 1,000 to 5,000, or even 7,500,
  • thiol-terminated poly( alkylene oxide) esters are readily prepared by the reaction of a polyhydric alcohol with an alkylene oxide followed by partial or complete esterification of the terminal hydroxyl groups with a mercaptocarboxylic acid.
  • suitable polyhydric alcohols include ethylene glycol, poly(oxyethylene) glycols, prepylene glycol, poly(oxypropylene) glycols, propane-l ,3-diol, poly(epichlorohydrin)s, butane-1,2- diol, butane-l ,3 -diol, butane-1,4-diol, butane-2,3-diol, poly(oxy-l, l-dimethylethylene) glycols, poly(tetrahydrofuran)s, glycerol, l,1,l-trimethylolethane, 1,1,1- trimethylolpropane, hexane-1,2,5-triol, hexane-1,2,6- triol, pentaerythritol, dipentaerythritol, mannitol, sorbitol, and adducts of alkylene oxides with ammonia or amines, such as di
  • Suitable alkylene 0xides include ethylene oxide, propylene oxide, tetrahydrofuran and, less preferably, epichlorohydrin. If desired, the polyhydric alcohol may be treated with one alkylene oxide, say propylene oxide, and then tipped with a different alkylene oxide, such as ethylene oxide.
  • the preferred mercaptocarboxylic acids for the esterification are, as already indicated, thioglycollic acid (2-mercaptoacetic acid) and 2-mercaptopropionic acid, but other mercaptomonocarbocylic acids which may be used include mercaptoundecylic acid and mercaptostearic acid.
  • the second class of thiol-terminated poly(alkylene oxides) includes those of formula i l l I (Oalkylene)- OH l R q I '(o-alk 1ene-)- OCHZCHCHZSH in which R denotes OHZ, --(O- alkylene) OH,O, CO, C H SH, or (O-alkylene) O.CO.C H Sl-l,
  • R,alkylene, m,p,q, and u have the meanings previously assigned
  • v is an integer of at least 1 and may have different values in each of the p chains.
  • the oxyalkylene units in the individual poly(oxyalhylene) chains may likewise be different, but are preferably the same, and may be substituted if desired, by, e.g., phenyl or chloromethyl groups.
  • ethers Preferred among such ethers are those which are also ings previously assigned, and further preferred are those of the formula in which R R and 12 also have the meanings previously assigned.
  • the particularly preferred ethers are of formula (OC H OCH THCH SH in which R t, m, and p have the meanings previously assigned.
  • the ethers of formula I in which R denotes Ol-l may be prepared in a known manner by reaction of an alkylene oxide with a polyhydric alcohol, etherification of the hydroxyl groups of the product with eipichlorohydrin, and treatment with sodium hydrosul phide to replace the chlorine by a sulphhydryl group (see US. Pat. No. 3,258,495, and United Kingdom Specification Nos. 1,076,725 and 1,144,761). In many cases the average number of thiol groups per molecule is not an integer but, for example, may be 2.6.
  • chlorohydrin ether obtained by reaction with epichlorohydrin may also react with epichlorohydrin, so forming an ether with contains two replaceable chlorine atoms per hydroxyl group originally present in the polyhydric alcohol Ethers of formula O c H H CHCH SH CH (oc H OCH where m has the meaning previously assigned, especially such ethers having a molecular weight within the range 700 to 3,500 or up to 7,500.
  • the ether-esters of formula 1 in which R denotes O.CO.C l-l ,,Sl-l or(O-alkylene) O.CO.C H ,,Sl-l are obtainable by esterification of the corresponding alcohol with a mercaptocarboxylic acid HOOCC l-l- Sl-l.
  • polythiols are insoluble in water but can be applied as aqueous dispersions or emulsions. They may also be applied from organic solvents, for example, lower alkanols such as ethyl alcohol, lower ketones such as ethyl methyl ketone, benzene, and halogenated hydrocarbon solvents, especially chlorinated and/or fiuorinated hydrc carbons containing not more than three carbon atoms, such as the dry-cleaning solvents, carbon tetrachloride, trichlorothylene, and perchloroethylene.
  • organic solvents for example, lower alkanols such as ethyl alcohol, lower ketones such as ethyl methyl ketone, benzene, and halogenated hydrocarbon solvents, especially chlorinated and/or fiuorinated hydrc carbons containing not more than three carbon atoms, such as the dry-cleaning solvents, carbon tetrachloride, t
  • the amount of the polythiol to be used depends on the effect desired. For most purposes from 0.1 to 10 percent by weight calculated on the weight of the material to be treated is preferred. The and, or handle, of the treated material will, of course, depend on the amount of polythiol employed and by simple experiment the least amount required to give the desired effect may readily be determined. Further, the composition of the fibres, and the construction of the fabrics, also influence the amount of polythiol required. Usually, a pick-up of from about 0.1 to 1 percent gives the required result.
  • nminoplasts When nminoplasts are employed in conjunction with the polythiols, they contain, per molecule, at least two groups of formula Cl-l OR directly attached to an amidic nitrogen atom or atoms, where R denotes a hydrogen atom, an alkyl group of from one to four carbon atoms, or an acetyl group.
  • R denotes a hydrogen atom, an alkyl group of from one to four carbon atoms, or an acetyl group.
  • aminoplasts are the N-hydroxymethyl, N-alkoxymethyl, and N-acetoxymethyl derivatives of the following amides and amide-like substances.
  • R denotes an alkyl or hydroxyalkyl group containing up to 4 carbon atoms
  • cyclic ureas examples include ethyleneurea (imidazolidin-Z-one), dihydroxyethyleneurea (4,5- dihydroxyimidazolidin-Z-one), hydantoin, uron (tetrahydro-oxadiazin-4-one), 1,2-propylenurea (4- methylimidazolidin-Z-one), 1,3-propyleneurea (hexahydro-2l-l-pyrimid-2-one), hydroxypropyleneurea 5-hydroxyhexahydro-ZH-pyrimid- 2-one) dimethylpropyleneurea (5,5- dimethylhexehydro-2H-pyrimid-2-one), dimethylhydroxypropyleneurea and dimethylmethoxypropyleneurea (i.e., 4-hydroxyand 4-methoxy-5,5- dimethylhexahydro-2l-l-pyrimid-2-one), and 5-ethyland 5-(2-hydroxyethyl)-triazin-2-one.
  • Carbonates and dicarbamates of aliphatic monohydric and dihydric alcohols containing up to four carbon atoms e.g., methyl, ethyl, isopropyl, 2- hydroxyethyl, Z-methyxthl,2-hydroxy-n-propyl, and 3- hydroxy-n-propyl carbamates, and ethylene and 1,4- butylene dicarbamates.
  • aminoplasts containing both N- hydroxymethyl and N-alkoxymethyl, or N- hydroxymethyl and N-acetoxymethyl groups may be used, for example, a hexamethylol melamine in which from 1 to 5 of the methylol groups have been so etherified or esterified.
  • the aminoplast is usually applied as such but, if desired, when a urea-formaldehyde or melamineformaldehyde product is to be used, it may be formed in situ in a conventional manner from a ureaformaldehyde concentrate or melamine-formaldehyde concentrate and the requisite additional urea or melamine.
  • aminoplasts employed are, in general, soluble in water and may be applied from aqueous solution; or they may be applied from aqueous emulsions, from solutions in the dry-cleaning solvents already mentioned, or from solutions in mixtures of water and a suitable cosolvent, such as methanol.
  • the proportions of the polythiol and the aminoplast can vary widely; usually there will be employed, per thiol group equivalent of the polythiol, from 2 to 50 or even 75, but usually from 5 to 40, N-methylol, N- alkoxymethyl or H-acetoxymethyl group equivalents of the aminoplast.
  • the desired effects may not be fully obtainable until substantially all the polythiol on the material has cured. At ordinary temperatures this may take from 5 to days or even longer.
  • the curing reaction can, however, be accelerated greatly by the use of a catalyst and generally it is preferred to add the catalyst to the material to be treated at the same time as the polythiol is applied, although it may be added before or afterwards if desired.
  • the curing time can be controlled by selecting an appropriate catalyst and the choice of curing time will depend on the particular application of the process according to the invention.
  • the catalysts may be bases, sicatives, sulphur, sulphur-containing organic compounds, and free-radical catalysts such as azodi-isobutyronitrile, peroxides and hydroperoxides, or combinations of these.
  • organic bases there may be used primary or secondary amines such as the lower alkanolamines, e.g., monoand di-ethanolamine, and lower alkylene polyamines, e.g., ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propane- ],2- and -l,3-diamine, and hexamethylenediamine.
  • organic bases there may be used the water-soluble oxides and hydroxide, e.g. sodium hydroxides, watersoluble, strongly basic salts such as trisodium phos phate, disodium tetraborate, and sodium carbonate, and also ammonia.
  • Sulphur-containing organic compounds which may be used as catalysts include those in which the sulphur atoms are not exclusively present as mercaptan groups, especially mercaptobenzothiazoles and their derivatives, dithiocarbamates, thiuram sulphides, thioureas, disulphides, alkyl xanthogen sluphides and alkyl xanthates.
  • siccatives are calcium, copper, iron, lead, cerium, and cobalt naphthenates.
  • Suitable peroxides and hydroperoxides are cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide, di-isopropyl peroxydicarbonate, and chlorobenzoyl peroxide.
  • Yet other catalysts are salts of a heavy metal with an acid having an acid strength (log pK) below 5 or chelates of a heavy metal, including chelates which are also salts.
  • heavy metal is meant one classified as heavy in Langes Handbook of Chemistry, revised 10th Edition, McGraw-I-Iill Book Co., at pp. 60 6l, that is, a metal of group IB, IIB, IIIB, lVB, VB, VIB, VIIB, or VIII, a metal of group IIIA having an atomic number of at least 13, a metal of group IVA having an atomic number of at least 32, or a metal of group VA having an atomic number of at least 51.
  • the metal is a member of group IB, IIB, IVB, VB, VIB, VIIB, or VIII, particularly the first series of such metals, i.e. titanium, vanadium, chromium, manganese, nickel, and especially iron, cobalt, and copper.
  • Suitable saltforming acids are mineral acids, especially hydrochloric, hydrobromic, nitric, sulphuric, phosphorous, and phosphoric acids, and organic acids such as chloroacetic, fumaric, maleic, oxalic, salicyclic, and, more especially, citric acid.
  • Suitable chelating agents include those in which the chelatingatoms are oxygen and/or nitrogen, for example, 1,2,- and 1,3-diketones such as acetylacetone, alkylenediamines such as ethylenediamine, and more particularly, ethylenediaminetetraacetic acid.
  • the amount of catalyst used can vary widely. In general from 0.1 to 20 percent, preferably 1 to 10 percent, by weight based on the weight of the polythiol used is required, although much larger quantities can be used.
  • Curing of the polythiol takes place more rapidly at a pH of more than 7, e.g., from 7.5 to 12. Curing is also assisted by using elevated temperatures, eg from 30 to 180C or even higher: thus, the threated fibres may be heated at a temperature of 35 to C, but temperatures of above 180 to as high as 220C, may be met with if curing is combined with heat-setting. In high humidities curing is also accelerated.
  • the aminoplast where one is added, may be cured under the usual conditions, i.e., at room temperature or at elevated temperatures. It may be desirable to include a catalyst for curing the aminoplast.
  • Catalysts which may be used include latent acid compounds (which may be metal salts), or mixtures thereof, or certain basic substances.
  • Ammonium salts which are latent acids, developing acidity in the mixture on heating include ammonium chloride, ammonium dihydrogen phosphate, ammonium sulphate and ammonium thiocyanate. These ammonium salts may be used admixed with metal salts which also have a similar catalytic effect.
  • Amine salts may also be used, e.g., 2-amino-2- methylpropanol hydrochloride.
  • suitable latent acid metal salts are zinc nitrate, zinc fluoroborate, zinc chloride, zirconium oxychloride, magnesium chloride, magnesium fluoroborate, or magnesium dihydrogen orthophosphate. These catalysts are generally used at concentrations of 0.3 to 5 percent by weight calculated on the weight of resin-forming materials of the aminoplast.
  • stronger acids such as hydrochloric or sulphuric acids which may be used as an aqueous solution (say, as 4- to 8- normal solutions) or which may be dissolved in a mixture of water and a solvent which is immiscible or partly miscible with water, and also acidic gases.
  • Basic substances which may be used include sodium bicarbonate and sodium carbonate.
  • the polythiol, and the catalyst if used, can be applied to the material in conventional ways.
  • fabrics or yarn may be padded on from a solution, emulsion, or suspension, or the material may be immersed in a bath. If garments or garment pieces are to be treated then it-is convenient to 1 1 spray them or to tumble them with the solution, emulsion, or suspension.
  • a particularly effective way of carrying out the process of this invention comprises immersing the fibres in an aqueous medium containing the polythiol and which is heated at a temperature in the range from to 95C. Exhaustion onto the fibres is favoured by working under slightly acid conditions, the aqueous medium having a pH in the range 3 to 6.
  • compositions used in the process of this invention may also contain antisoiling, antistatic, bacteriostatic, rotproofing, flameproofing, or wetting agents. They may also contain water-repellents such as paraffin wax, of fluoroscent whitening agents.
  • the following Examples illustrate the invention. Unless otherwise specified, parts and percentages are by weight.
  • the thiols used were prepared as follows: Thiol A A mixture of 800 g (0.2 g-mol) of a polyoxpropylene triol having an average molecular weight 4,000 and made from glycerol and propylene oxide (Polyol A), 55.2 g (0.6 g-mol.) of thioglycollic acid, 5 g of toluenep-sulphonic acid, and 350 ml of toluene was heated to reflux with stirring for 4 hours in an atmosphere of nitrogen. Water (108 ml, 0.6 g-mol).
  • Emulsion A An aqueous emulsion of this thiol was then prepared.
  • Emulsion A ture of C and C aliphatic primary amines 1 mole.) with ethylene oxide (70 mols.). This stock emulsion was then diluted with 99 parts of water to form Emulsion A.
  • Thiol B Thiol M is similar to Thiol B, but the glycerolpropylene oxide adduct used as the polyol had an average molecular weight of 700: Thiol M had a mercaptan content of 2.17 equiv./kg, corresponding to 2.3 SH groups per average molecule.
  • Emulsions C M were made as described for Emulsion A, substituting the same weight of the corresponding polythiol.
  • Emulsion Z used for purposes of comparison, was made by substituting a polyoxypropylene trio] of average molecular weight 4,000 (Polyol A) for Polythiol A.
  • Emulsions N and O Emulsions N and 0 were prepared from Thiols A and G respectively, by mixing at room temperature with a Silverson mixer the following:
  • the staining test referred to in the Examples con' sisted of immersing the patterns in an aqueous solution, containing 2 g/l iodine and 20 g/l potassium iodide at room temperature for 30 seconds. The samples were washed in water for 10 seconds, pressed between filter papers to remove excess water, and then allowed to stand at room temperature for about 10 minutes. Staining was then assessed using the grey scale (British Standard 3.8. 2666: 1961 ISO Recommendation R /l/Part 3); a value of 5 denotes no change in colour, and l denotes a complete loss in colour, corresponding to no removal, and to complete removal, of the polythiol.
  • EXAMPLE 1 An impregnation liquor was prepared by adding 10 ml of Emulsion A to ml of water. The liquor was heated to 60C and a 10 g hank of yarn composed of short staple fibres of the polyester, polyethylene, terephthalate, was added. The temperature of the liquor was maintained at 60C for 30 minutes with continual movement of the yarn in the liquor by means of a glass EXAMPLE 4 An impregnation liquor was prepared, comprising the following:
  • EXAMPLE 2 The yarn was continually moved in the liquor and, after Three impregnation liquors were prepared, each being removed, it was spun in a spin dryer and dried at comprising the following: 70C.
  • the impregnation liquor was virtually clear on removal of the hank, showing that almost complete exhaustion of the polythiol had occured.
  • the yarn so EmulSiQnA m1 treated possessed a greatly improved handle, which monoethanolamine, 1% aqueous solution 5 ml water 175 ml 20 may be described as soft and silky.
  • Thiols A and B were applied to a variety of yarns from perchloroethylene solution.
  • the yams were dipped into perchloroethylene solutions of the thiol at room temperature: the solutions also contained diethylenetriamine as catalyst.
  • the yarns were then centrifuged so as to leave 1 percent by weight of the thiol and 0.02 percent by weight of diethylenetriamine. After being dried in an oven at 60C, the yarns were allowed to stand overnight in an atmosphere of 66 percent relative humidity at 20C before the handle was assessed according to the following classification:
  • Fixation of the thiol was then assessed by either washing the patterns in water at 60C for 10 minutes containing 1 percent of a nonionic detergent or boiling them in hexane for 10 minutes, then staining the unwashed and washed patterns in iodine and assessing the difference in staining.
  • Emulsion A ( g) 20 20. 20 20 2O 20 2O 20 Aqueous acetic acid 5% (ml) 4 4 4 4 4 4 4 4 Aqueous hydrogen peroxide 20 vol strength (ml) 15 10 5 2 l Aqueous copper sulphate ml 2.5 Aqueous ferric Chloride 1% (ml) 2.5 Water (ml) 176 161 166 171 I74 175 173.5 173.5 Assessment of iodine staining after (a) washing in water at 60C 2 5 5 5 2-3 2 4 3-4 (b) boiling in hexane l-2 5 5 5 5 l-2 l-2 3-4 2 EXAMPLE 8 EXAMPLE 1O This Example illustrates that the polyoxypylene triol used to prepare Thiol A had negligible effect on the fibres. Emulsions A and Z were applied to scoured Crimplene fabric at a liquor ratio of 20:1, using thefollowing impregnation liquors.
  • Emulsion A or Emulsion Z Water 20 g 180 ml.
  • EXAMPLE 9 This Example illustrates the enhanced degree of fixation obtained when catalysts for curing Emulsion A are incorporated in the treatment bath.
  • Application Ii- Aqueous liquors containing Emulsions A,C,D,E,F, and G were applied to scoured Crimplene, the liquors containing 1%(on weight of Crimplene) of each of the thiols.
  • the pH of the liquors was adjusted to 3.5 with acetic acid, and treatment was carried out at a liquor ratio of 20:1 for 30 minutes at C. After 15 minutes hydrogen peroxide was added to the liquor so that a 1 volume concentrations resulted.
  • the liquors gradually cleared from their initial white milky appearance.
  • the patterns were spun in a spin dryer without being rinsed, and dried in an oven at 60C for 30 minutes. They were then conditioned overnight in an atmosphere of 66 percent relative humidity and at 20C before assessments of handle were carried out.
  • Thiols E, F and G imparted on extremely soft and pleasant handle to the Crimplene, Thiols A and D gave a very soft handle, while with Thiol C the handle was considerably softer than that of untreated material.
  • EXAMPLE 1 l Thiol A is extremely fast to washing treatments when applied to Crimplene, as shown by the following. Thiol A was applied as in Example 10 to scoured Crimplene, the treated patterns were allowed to condition for 3 days at room temperature and 66 percent relative humidity, and the fastness of the finish was then assessed by washing. The excellent fastness properties of the finish are shown by the fact that there was no difference in handle or in degree of iodine staining between washed and unwashed patterns after the following washing treatments:
  • washings were carried out for minutes at 40, 70, and 100C.
  • the treated patterns were unaffected by simulated perspiration tests at pH 5.5 and 8.0.
  • EXAMPLE l2 In this Example the finish is applied under acidic conditions to obtain optimum exhaustion onto the fibres and then the pH of the liquor is made alkaline to obtain maximum fixation and curing of the thiol.
  • Crimplene was treated at a liquor ratio of 20:1 with a diluted aqueous suspension of Emulsion A (100 g/l) set at pH 4.0 with acetic acid, the fabric being immersed at 60C: during the course of minutes the liquor substantially cleared losing its initial milky-white appearance.
  • the liquor was then adjusted to pH 8.5 or 10.0 by addition of either 3.5 g/l disodium phosphate dodecahydrate 1.5 g/l trisodium phosphate dodecshydrate 2.5 g/l disodium phosphate dodecahydrate 2.5 g/l trisodium phosphate dodecahydrate respectively,
  • EXAMPLE l3 Aqueous liquors containing emulsions A,E, and G-M were applied to a scoured coarse polyester yarn, the liquors containing 1 percent (on the weight of the fibre) of each of the thiols.
  • the pH of the liquors was adjusted to 4.0 with acetic acid and treatment was carried out at a liquor ratio of :1 for 30 minutes at 60C. After 15 minutes, hydrogen peroxide was added to the liquor so that a 1 volume concentration resulted.
  • the liquors which initially were milky white, gradually cleared.
  • the patterns were spun in a spin dryer and dried in an oven at 60C for 30 minutes. They were then conditional overnight in an atmosphere of 66 percent relative humidity and at 20C.
  • Emulsion A was diluted with water, and acetic acid was added in some cases. Samples (10 g) of Crimplene fabric were treated with these liquors for 15 minutes at 60C using a liquor ratio of 20:1. The curing catalysts which were solids rapidly dissolved when added to the bath. Treatment was continued for a further 15 minutes under the above conditions, and the fabric samples were then spun in a spin dryer without rinsing and dried in an oven at 55C for 30 minutes.
  • a 50:50 polyester-cotton blend plain weave fabric was padded with one of liquors a, b, or c to 70 percent pick-up, dried at its original dimensions on tenter frames at 60C, and heated for 5 minutes at C.
  • the dry crease angles of the fabric samples were determined by the Monsanto method, 12 speciments (six folded warpwise, six folded weftwise) being used in each test, the specimens were creased under a 2 kg load for 3 minutes and and allowed to hang, suspended over a wire, for 3 minutes before the crease angles were measured. The values given below are the average of the six obtained by adding the warpwise value to the corresponding weftwise value and dividing by two.
  • Tear strengths were determined by the Elmendorf method according to TAPPl Standard T 414 n-49. Three samples, each 63 X 63 mm, were used, and the tear strengths were measured in the warp direction. In
  • Aminoplast denotes a 50 percent aqueous solution of bis(N-hydroxymethyl) dihydroxyethyleneurea.
  • a g piece of scoured Crimplene fabric was treated with a liquor comprising Emulsion A g Aqueous acetic acid (5%) 4 ml Water 176 ml EXAMPLE 17
  • This Example illustrates that soil-release properties and improved resistance to soil-redeposition can be imparted by the thiol emulsions.
  • Crimplene fabric was treated by the method of Example 15, but was not heatset. Samples of treated and untreated fabric were then screen-printed in a striped pattern with three different soiling compositions, each applied as a band 3 cm wide and separated from the adjoining band by an unsoiled strip of the same width.
  • Soil A is a mixture of used dirty motor oil (50 percent) and petroleum jelly (50 percent).
  • Soil B is a solution of lanolin (84 percent) and trichloroethylene (16 percent).
  • Soil C is a mixture of sieved vacuum cleaner dust (20 percent), lanolin (60 percent), and trichloroethylene (20 percent).
  • the treated patterns were dried in an oven for 2 hours at 35C. Portions of the treated and untreated soiled fabric were then washed for minutes at 40C in a washing machine with a solution of 5 g/l of an anionic detergent.
  • the treated sample lost nearly all of each of the soils on washing and there was virtually no soil redeposition on the un-soiled portions of the fabric.
  • the untreated 6 pattern retained a considerable portion of the soil during washing and there was widespread deposition of soil on the un-soiled regions of the fabric.
  • a process for modifying synthetic fibres which comprises 1. treating the fibres, in the absence of keratinous 5 material, with a polythiol having two to six thiol groups per molecule and a molecular weight between about 400 and about 10,000 wherein the polythiol has the formula r w I I T-(O-alkylene) m OH 20 in which m is a positive integer of at least 1,
  • n zero of 1
  • p is a positive integer of at least 2 and at most 6,
  • q is zero or a positive integer of four or less, selected 25 so that (p+q) equals at least 2 and at most 6,
  • each alkylene group contains a chain of at least 2 and at most 6 carbon atoms between consecutive oxygen atoms
  • R is an aliphatic radical containing at least 2 carbon 0 atoms
  • X is an aliphatic radical containing at least one thiol group and 2. curing the polythiol on the fibres.
  • p is 2 to 6, provided that when q is 1, p is 2,
  • R is an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms
  • X is an aliphatic radical of the formula C H SI-I
  • u is 1 or 2.
  • I is an integer of at least 2 and at most 3, u is a positive integer of at most 2 and m has the meaning given in claim 1.
  • the alkylene groups are C l-l and the average molecular weight is between about 700 and about 7,500.
  • a catalyst for curing the polythiol is also applied, said catalyst being selected from the group consisting of hoses, siccatives, sulphur, sulphur-containing organic compounds in which the sulphur atoms are not exclusively present as mercaptan groups, free-radical catalysts, salts of heavy metals with acids having an acid strenght (pKl) below 5, and chelates of heavy metals.
  • the synthetic fibres are selected from the group comprising fibres of nylon, polyester, polyacrylonitrile, and polyvinyl alcohol.
  • Synthetic fibrous material free from keratinous material, bearing thereon from 0.l to 10 percent by 23 weight of a polythiol resin having 2 to 6 thiol groups per molecule and a molecular weight between about 400 and about 10,000, the polythiol having the formula:
  • n zero or 1
  • p is a positive integer of at least 2 and at most 6,
  • q is zero or a positive intefer of four or less, selected so that (p+q) equals at least 2 and at most 6,
  • each alkylene group contains a chain of at least 2 and at most 6 carbon atoms between consecutive oxygen atoms
  • R is an aliphatic radical containing at least 2 carbon atoms
  • X is an aliphatic radical containing at least one thiol group.
  • p is 2 to 6, provided that when q is l, p is 2 R is an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms, and
  • X is an aliphatic radical of the formula C H SH
  • u is 1 or 2.
  • polythiol is selected from the formula:
  • I. is an integer of at least 2 and at most 3,
  • u is a positive integer of at most 2 and m has the meaning defined in claim 17.
  • n is Zero
  • X is an aliphatic radical of the formula the alkylene groups are C l-l and the average weight is between about 700 and about 7,500.
  • the polythiol is of th formula (OC H O.CO.C H SH (OC H O.CO.C H Sl-l wherein a is 2, t is 4 and u is l, and m has the meaning defined in claim 17.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
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US37540873 1970-07-02 1973-07-02 Treatment of fibres Expired - Lifetime US3881047A (en)

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Application Number Priority Date Filing Date Title
GB3224170A GB1358837A (en) 1970-07-02 1970-07-02 Treatment of fibres and the fibres thus treated
CH952571D CH952571A4 (enrdf_load_stackoverflow) 1970-07-02 1971-06-29
CH952571A CH547894A (enrdf_load_stackoverflow) 1970-07-02 1971-06-29
DE19712132535 DE2132535A1 (de) 1970-07-02 1971-06-30 Behandlung von synthetischen Fasern
FR7124053A FR2100853B1 (enrdf_load_stackoverflow) 1970-07-02 1971-07-01
AT570571A AT322494B (de) 1970-07-02 1971-07-01 Verfahren zur veredlung von synthetischen fasern
NL7109109A NL7109109A (enrdf_load_stackoverflow) 1970-07-02 1971-07-01
BE769410A BE769410A (fr) 1970-07-02 1971-07-02 Traitement de fibres
CA117,208A CA967710A (en) 1970-07-02 1971-07-02 Treatment of fibres
US37540873 US3881047A (en) 1970-07-02 1973-07-02 Treatment of fibres

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GB3224170A GB1358837A (en) 1970-07-02 1970-07-02 Treatment of fibres and the fibres thus treated
US15855571A 1971-06-30 1971-06-30
US37540873 US3881047A (en) 1970-07-02 1973-07-02 Treatment of fibres

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CA (1) CA967710A (enrdf_load_stackoverflow)
CH (2) CH952571A4 (enrdf_load_stackoverflow)
DE (1) DE2132535A1 (enrdf_load_stackoverflow)
FR (1) FR2100853B1 (enrdf_load_stackoverflow)
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4232087A (en) * 1978-08-03 1980-11-04 Albany International Corp. Method of coating organic fibers with polytetrafluoroethylene
US4861863A (en) * 1986-10-31 1989-08-29 Henkel Kommanditgesellschaft Auf Aktien Process for the production and purification of SH-terminated prepolymers and use thereof
US5296269A (en) * 1993-03-03 1994-03-22 The Board Of Trustees Of The University Of Illinois Process for increasing the crease resistance of silk textiles
US5669937A (en) * 1996-03-07 1997-09-23 Milliken Research Corporation Method to remove iodine stain
US6547832B1 (en) * 1997-10-03 2003-04-15 Clariant Finance (Bvi) Limited Finishing for jeans material
US20050014436A1 (en) * 2000-10-13 2005-01-20 Michael Brier Process for producing fabric articles having water-resistant and/or antimicrobial characteristics
US20090186988A1 (en) * 2008-01-22 2009-07-23 Ppg Industries Ohio, Inc. Modified aminoplast crosslinkers and coating compositions containing such crosslinkers
US20100041839A1 (en) * 2008-08-13 2010-02-18 Ppg Industries Ohio, Inc. Lightweight particles and compositions containing them
US9902799B2 (en) 2015-11-11 2018-02-27 Prc-Desoto International, Inc. Urethane-modified prepolymers containing pendent alkyl groups, compositions and uses thereof

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US3258495A (en) * 1962-10-24 1966-06-28 Diamond Alkali Co Thiol terminated polyoxyalkylene glycols
US3278496A (en) * 1961-03-01 1966-10-11 Diamond Alkali Co Thiol terminated liquid polymers
US3431239A (en) * 1965-03-29 1969-03-04 Prod Res & Chem Corp Mercaptan terminated polyethers
US3465057A (en) * 1965-02-22 1969-09-02 Ciba Ltd Curable ester compositions
US3645781A (en) * 1968-07-15 1972-02-29 Iws Nominee Co Ltd Treatment of keratinous fibers and fabrics
US3676195A (en) * 1969-07-29 1972-07-11 Grace W R & Co Water-resistant materials,and methods of production and use of same

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
FR20146E (fr) * 1916-10-06 Maurice Meunier Récepteur téléphonique haut parleur

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Publication number Priority date Publication date Assignee Title
US3278496A (en) * 1961-03-01 1966-10-11 Diamond Alkali Co Thiol terminated liquid polymers
US3258495A (en) * 1962-10-24 1966-06-28 Diamond Alkali Co Thiol terminated polyoxyalkylene glycols
US3465057A (en) * 1965-02-22 1969-09-02 Ciba Ltd Curable ester compositions
US3431239A (en) * 1965-03-29 1969-03-04 Prod Res & Chem Corp Mercaptan terminated polyethers
US3645781A (en) * 1968-07-15 1972-02-29 Iws Nominee Co Ltd Treatment of keratinous fibers and fabrics
US3676195A (en) * 1969-07-29 1972-07-11 Grace W R & Co Water-resistant materials,and methods of production and use of same

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4232087A (en) * 1978-08-03 1980-11-04 Albany International Corp. Method of coating organic fibers with polytetrafluoroethylene
US4861863A (en) * 1986-10-31 1989-08-29 Henkel Kommanditgesellschaft Auf Aktien Process for the production and purification of SH-terminated prepolymers and use thereof
US5296269A (en) * 1993-03-03 1994-03-22 The Board Of Trustees Of The University Of Illinois Process for increasing the crease resistance of silk textiles
US5669937A (en) * 1996-03-07 1997-09-23 Milliken Research Corporation Method to remove iodine stain
US6547832B1 (en) * 1997-10-03 2003-04-15 Clariant Finance (Bvi) Limited Finishing for jeans material
US20050014436A1 (en) * 2000-10-13 2005-01-20 Michael Brier Process for producing fabric articles having water-resistant and/or antimicrobial characteristics
US20090186988A1 (en) * 2008-01-22 2009-07-23 Ppg Industries Ohio, Inc. Modified aminoplast crosslinkers and coating compositions containing such crosslinkers
KR101288259B1 (ko) * 2008-08-13 2013-07-26 피피지 인더스트리즈 오하이오 인코포레이티드 경량 입자 및 경량 입자를 포함하는 조성물
US20100286307A1 (en) * 2008-08-13 2010-11-11 Ppg Industries Ohio, Inc. Lightweight particles and compositions containing them
CN102143997A (zh) * 2008-08-13 2011-08-03 Ppg工业俄亥俄公司 轻质颗粒以及含有它们的组合物
US20100041839A1 (en) * 2008-08-13 2010-02-18 Ppg Industries Ohio, Inc. Lightweight particles and compositions containing them
US8816023B2 (en) * 2008-08-13 2014-08-26 Ppg Industries Ohio, Inc Lightweight particles and compositions containing them
US8993691B2 (en) 2008-08-13 2015-03-31 Ppg Industries Ohio, Inc. Lightweight particles and compositions containing them
CN104130746B (zh) * 2008-08-13 2016-11-02 Ppg工业俄亥俄公司 轻质颗粒以及含有它们的组合物
US9951251B2 (en) 2008-08-13 2018-04-24 Ppg Industries Ohio, Inc. Lightweight particles and compositions containing them
US10308837B2 (en) 2008-08-13 2019-06-04 Ppg Industries Ohio, Inc. Lightweight particles and compositions containing them
US10759965B2 (en) 2008-08-13 2020-09-01 Ppg Industries Ohio, Inc. Lightweight particles and compositions containing them
US11292937B2 (en) 2008-08-13 2022-04-05 Ppg Industries Ohio, Inc. Lightweight particles and compositions containing them
US9902799B2 (en) 2015-11-11 2018-02-27 Prc-Desoto International, Inc. Urethane-modified prepolymers containing pendent alkyl groups, compositions and uses thereof
US11091582B2 (en) 2015-11-11 2021-08-17 Prc-Desoto International, Inc. Urethane-modified prepolymers containing pendent alkyl groups, compositions and uses thereof

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Publication number Publication date
CH547894A (enrdf_load_stackoverflow) 1974-04-11
CA967710A (en) 1975-05-20
NL7109109A (enrdf_load_stackoverflow) 1972-01-04
DE2132535A1 (de) 1972-01-13
CH952571A4 (enrdf_load_stackoverflow) 1973-08-15
FR2100853A1 (enrdf_load_stackoverflow) 1972-03-24
BE769410A (fr) 1972-01-03
GB1358837A (en) 1974-07-03
AT322494B (de) 1975-05-26
FR2100853B1 (enrdf_load_stackoverflow) 1974-09-06

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